CN115779890B - Preparation method of manganese-based electrothermal catalyst for toluene purification - Google Patents
Preparation method of manganese-based electrothermal catalyst for toluene purification Download PDFInfo
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Abstract
The invention relates to the technical field of industrial VOCs organic waste gas purification, in particular to a preparation method of a manganese-based electrothermal catalyst for toluene purification, which comprises the following steps: s1, directly mixing and dissolving manganese salt, indium salt and tin salt in a certain proportion into deionized water to obtain a mixed solution A; s2, adding a certain amount of potassium permanganate into the mixed solution A obtained in the step S1, and stirring and reacting for a period of time to obtain a mixed solution B; s3, regulating and controlling the pH value of the mixed solution B obtained in the step S2 by using a pH regulator, and stirring and reacting for a period of time to obtain a precipitate; and S4, placing the precipitate obtained in the step S3 into a muffle furnace for calcination, heating to a certain temperature at a certain heating rate, and maintaining for a period of time to obtain the manganese-based electrothermal catalyst. The preparation process is simple, the conductive and catalytic oxidation dual-function effect of the catalyst is realized, and the manganese-based electrothermal catalyst prepared by the method has good application prospect and economic benefit in the field of industrial VOCs flue gas purification.
Description
Technical Field
The invention relates to the technical field of industrial VOCs organic waste gas purification, in particular to a preparation method of a manganese-based electrothermal catalyst for toluene purification.
Background
In recent years, PM2.5 and ozone concentration in many areas of China exceed the standard, and severe haze weather is caused. Volatile organic pollutants VOCs are important precursors of PM2.5 and ozone, and emission reduction and control of the VOCs are necessary means for atmospheric environmental management. Among the VOCs treatment technologies, the catalytic reduction oxidation technology has the characteristics of small energy consumption, small secondary pollution and the like, and can convert the VOCs into water and carbon dioxide, so that the catalytic reduction oxidation technology is widely promoted. However, the existing catalytic oxidation technology is a traditional thermal catalytic method for heating gas and catalyst by external heat, and has the problems of high energy consumption, uneven heating of the catalyst, high activation temperature of the catalyst and the like.
There has recently been great interest in the oxidation of VOCs by electrothermal catalysis. Mortens et al greatly improve catalyst utilization and limit unwanted by-product formation by directly integrating an electrically heated catalytic Structure for Methane Reforming (SMR) hydrogen production reactions [ Sebastin T. Wismann, et al, electric methane reforming: A compact approach to greener industrial hydrogen production, science,2019,364:756-759]. Zou et al electrically driven MnO supported on carbon cloth 2 Realizes the efficient removal of formaldehyde [ Nan Zou, et al, electric thermal regeneration by Joule heat effect on carbon cloth based ] MnO 2 catalyst for long-term formaldehyde removal,Chemical Engineering Journal,2019,357:1-10.]. However, for the efficient energy-saving electrothermal catalytic oxidation technology of benzene series VOCs (such as toluene) which have larger engineering existence amount and are difficult to remove, the realization of efficient removal through electrothermal driving is not reported to date because of the requirement of higher low-temperature electrothermal catalytic activity.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a preparation method of a manganese-based electrothermal catalyst for purifying toluene, which breaks through the low-temperature low-efficiency dilemma of the traditional thermal catalyst by synthesizing conductive metal oxide, realizes the self-heat release of the catalyst and improves the purifying effect of the benzene VOCs by low-temperature catalytic oxidation.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the manganese-based electrothermal catalyst for toluene purification comprises the following specific steps:
s1, directly mixing and dissolving manganese salt, indium salt and tin salt in a certain proportion into deionized water to obtain a mixed solution A;
s2, adding a certain amount of potassium permanganate into the mixed solution A obtained in the step S1, and stirring and reacting for a period of time to obtain a mixed solution B;
s3, regulating and controlling the pH value of the mixed solution B obtained in the step S2 by using a pH regulator, and stirring and reacting for a period of time to obtain a precipitate;
and S4, placing the precipitate obtained in the step S3 into a muffle furnace for calcination, heating to a certain temperature at a certain heating rate, and maintaining for a period of time to obtain the manganese-based electrothermal catalyst.
Preferably, in step S1, the manganese salt is one or a mixture of several of manganese nitrate, manganese chloride, manganese acetate and manganese sulfate.
Preferably, in step S1, the indium salt is one or more of indium chloride, indium nitrate, indium sulfate, and indium acetate.
Preferably, in step S1, the tin salt is one or more of solid tin acetate, tin sulfate, stannous chloride and tin nitrate.
Preferably, in the step S1, the molar ratio of manganese salt, indium salt, tin salt and deionized water is 10 (1-5): 5-1): 1000-6000.
Preferably, in the step S2, the molar ratio of the potassium permanganate to the manganese salt in the step S1 is as follows: 1, stirring time is 10-120 min, and stirring speed is 100-1000 r/min.
Preferably, in the step S3, the pH regulator is one or a mixture of sodium hydroxide, potassium hydroxide, ammonia water and sodium ethoxide, the pH regulating range is 9-13, the stirring time is 10-120 min, and the stirring speed is 100-1000 r/min.
Preferably, in the step S4, the calcination temperature rising rate is 1-10 ℃/min, the constant temperature maintained by calcination is 100-500 ℃, and the maintaining time of the calcination constant temperature stage is 1-12 h.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention synthesizes the conductive metal oxide catalyst and takes the catalyst as a catalytic material of toluene VOC, directly utilizes the low voltage to promote the conductive catalyst to emit heat, thereby greatly reducing the activation temperature of the catalyst and providing the application of the catalyst in the electrothermal catalytic oxidation of toluene.
2. The raw materials are easy to obtain, and the preparation method is simple; the prepared catalyst has good conductivity and high activity of catalyzing and oxidizing benzene VOCs at low temperature; compared with the use of traditional thermocatalytic materials, the method has better energy conservation.
Drawings
FIG. 1 is an XRD pattern of a low-temperature high-activity manganese-based electrothermal catalyst prepared in example 1 of the present invention;
FIG. 2 is a graph showing the comparison of the catalytic oxidation performance of toluene under the conditions of 8V voltage and no power supply of the low-temperature high-activity Mn-based catalyst electrothermal catalyst prepared in example 1 of the present invention.
Detailed Description
The following technical solutions in the embodiments of the present invention will be clearly and completely described with reference to the accompanying drawings, so that those skilled in the art can better understand the advantages and features of the present invention, and thus the protection scope of the present invention is more clearly defined. The described embodiments of the present invention are intended to be only a few, but not all embodiments of the present invention, and all other embodiments that may be made by one of ordinary skill in the art without inventive faculty are intended to be within the scope of the present invention.
Example 1:
(1) Directly dissolving 10mmol of manganese nitrate, 5mmol of indium nitrate and 1mmol of stannous chloride into 2500mmol of deionized water to obtain a mixed solution A;
(2) Stirring the mixed solution A in step (1) at 300r/min, slowly adding 50mmol potassium permanganate into the mixed solution A, and continuously stirring for 30min to obtain a mixed solution B;
(3) Regulating the pH value of the mixed solution B in the step (2) to 10 by using NaOH, and continuously stirring for 30min at 300r/min to obtain a precipitate;
(4) Calcining the precipitate obtained in the step (3) in a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min, and maintaining the temperature for 3 hours to obtain the product, namely the manganese-based electrothermal catalyst.
As can be seen from the XRD pattern of the manganese-based electrothermal catalyst prepared in fig. 1, the mixed crystal forms of manganese oxide, tin oxide and indium oxide appear in the XRD pattern of the prepared catalyst, and the structure ensures high conductivity and high electrothermal catalytic activity of the catalyst.
As can be seen from the graph of the electrothermal catalytic oxidation effect of the manganese-based electrothermal catalyst prepared in FIG. 2 on 1000ppm toluene, the removal efficiency of the catalyst on toluene can be greatly improved under the condition of low voltage.
200mg of the manganese-based electrothermal catalyst prepared in example 1 was taken and T of the electrothermal catalytic oxidation of toluene was measured 20％ 、T 50％ And T 90％ The toluene removal activity was excellent when 84 ℃, 117 ℃ and 176 ℃ were reached, respectively.
Example 2:
(1) Directly dissolving 10mmol of manganese chloride, 1mmol of indium chloride and 5mmol of tin nitrate into 1000mmol of deionized water to obtain a mixed solution A;
(2) Stirring the mixed solution A in step (1) at 100r/min, slowly adding 1mmol of potassium permanganate into the mixed solution A, and continuously stirring for 10min to obtain a mixed solution B;
(3) Regulating the pH value of the mixed solution B in the step (2) to 9 by NaOH, and continuously stirring for 10min at 100r/min to obtain a precipitate;
(4) Calcining the precipitate obtained in the step (3) in a muffle furnace, heating to 100 ℃ at a heating rate of 1 ℃/min, and maintaining the temperature for 12 hours to obtain the product, namely the manganese-based electrothermal catalyst.
200mg of T for the electrothermal catalytic oxidation of toluene by using the manganese-based electrothermal catalyst prepared in embodiment 2 20％ 、T 50％ And T 90％ The toluene removal activities were excellent when 120 ℃, 156 ℃ and 210 ℃ were reached, respectively.
Example 3:
(1) Directly dissolving 10mmol of manganese acetate, 2mmol of indium acetate and 4mmol of tin acetate into 1500mmol of deionized water to obtain a mixed solution A;
(2) Stirring the mixed solution A in step (1) at 200r/min, slowly adding 2mmol of potassium permanganate into the mixed solution A, and continuously stirring for 20min to obtain a mixed solution B;
(3) Regulating the pH value of the mixed solution B in the step (2) to 11 by NaOH, and continuously stirring for 20min at 200r/min to obtain a precipitate;
(4) Calcining the precipitate obtained in the step (3) in a muffle furnace, heating to 200 ℃ at a heating rate of 3 ℃/min, and maintaining the temperature for 10 hours to obtain the product, namely the manganese-based electrothermal catalyst.
200mg of T for the electrothermal catalytic oxidation of toluene by using the manganese-based electrothermal catalyst prepared in embodiment 3 20％ 、T 50％ And T 90％ The toluene removal activities were excellent when 110 ℃, 143 ℃ and 197 ℃ were achieved, respectively.
Example 4:
(1) Directly dissolving 10mmol of manganese sulfate, 1.5mmol of indium sulfate and 3mmol of tin sulfate into 2000mmol of deionized water to obtain a mixed solution A;
(2) Stirring the mixed solution A in step (1) at 400r/min, slowly adding 3mmol of potassium permanganate into the mixed solution A, and continuously stirring for 40min to obtain a mixed solution B;
(3) Regulating the pH value of the mixed solution B in the step (2) to 12 by NaOH, and continuously stirring at 400r/min for 40min to obtain a precipitate;
(4) Calcining the precipitate obtained in the step (3) in a muffle furnace, raising the temperature to 300 ℃ at a heating rate of 4 ℃/min, and maintaining the temperature for 8 hours to obtain the product, namely the manganese-based electrothermal catalyst.
200mg of T for the electrothermal catalytic oxidation of toluene by using the manganese-based electrothermal catalyst prepared in embodiment 4 20％ 、T 50％ And T 90％ The toluene removal activity was excellent when 102 ℃, 131 ℃ and 192 ℃ were reached, respectively.
Example 5:
(1) Directly dissolving 5mmol of manganese nitrate, 5mmol of manganese sulfate, 2mmol of indium nitrate, 1mmol of indium sulfate, 1mmol of tin nitrate and 1mmol of tin sulfate into 3000mmol of deionized water to obtain a mixed solution A;
(2) Stirring the mixed solution A in the step (1) at 500r/min, slowly adding 4mmol potassium permanganate into the mixed solution A, and continuously stirring for 50min to obtain a mixed solution B;
(3) Regulating the pH value of the mixed solution B in the step (2) to 13 by NaOH, and continuously stirring at 500r/min for 50min to obtain a precipitate;
(4) Calcining the precipitate obtained in the step (3) in a muffle furnace, heating to 500 ℃ at a heating rate of 6 ℃/min, and maintaining the temperature for 6 hours to obtain the product, namely the manganese-based electrothermal catalyst.
200mg of T for the electrothermal catalytic oxidation of toluene by using the manganese-based electrothermal catalyst prepared in embodiment 5 20％ 、T 50％ And T 90％ The temperatures of 91 ℃, 121 ℃ and 184 ℃ are respectively reached, and excellent toluene removal activity is shown.
Example 6:
(1) Directly dissolving 4mmol of manganese nitrate, 4mmol of manganese sulfate, 2mmol of manganese acetate, 1mmol of indium acetate, 2mmol of indium nitrate, 1mmol of indium sulfate, 0.5mmol of tin nitrate, 0.25mmol of tin acetate and 0.25mmol of tin sulfate into 3500mmol of deionized water to obtain a mixed solution A;
(2) Stirring the mixed solution A in the step (1) at 600r/min, slowly adding 6mmol potassium permanganate into the mixed solution A, and continuously stirring for 60min to obtain a mixed solution B;
(3) Regulating the pH value of the mixed solution B in the step (2) to 13 by NaOH, and continuously stirring at 600r/min for 60min to obtain a precipitate;
(4) Calcining the precipitate obtained in the step (3) in a muffle furnace, raising the temperature to 450 ℃ at the heating rate of 7 ℃/min, and maintaining the temperature for 4 hours to obtain the product, namely the manganese-based electrothermal catalyst.
200mg of T for the electrothermal catalytic oxidation of toluene by using the manganese-based electrothermal catalyst prepared in embodiment 6 20％ 、T 50％ And T 90％ The toluene removal activities were excellent when 86 ℃, 119 ℃ and 183 ℃ were obtained, respectively.
Example 7:
(1) Directly dissolving 10mmol of manganese nitrate, 3mmol of indium nitrate, 1mmol of indium sulfate, 1mmol of tin nitrate and 2mmol of tin acetate into 6000mmol of deionized water to obtain a mixed solution A;
(2) Stirring the mixed solution A in step (1) at 1000r/min, slowly adding 10mmol potassium permanganate into the mixed solution A, and continuously stirring for 120min to obtain a mixed solution B;
(3) Regulating the pH value of the mixed solution B in the step (2) to 10 by NaOH, and continuously stirring at 1000r/min for 120min to obtain a precipitate;
(4) Calcining the precipitate obtained in the step (3) in a muffle furnace, heating to 500 ℃ at a heating rate of 10 ℃/min, and maintaining the temperature for 1h to obtain the product, namely the manganese-based electrothermal catalyst.
200mg of T for the electrothermal catalytic oxidation of toluene by using the manganese-based electrothermal catalyst prepared in example 7 20％ 、T 50％ And T 90％ The temperatures of 131 ℃, 163 ℃ and 211 ℃ are respectively reached, and excellent toluene removal activity is shown.
Comparative example 1: the preparation method of the manganese oxide comprises the following steps:
(1) Directly dissolving 10mmol of manganese nitrate into 2500mmol of deionized water to obtain a mixed solution A;
(2) Stirring the mixed solution A in step (1) at 300r/min, slowly adding 50mmol potassium permanganate into the mixed solution A, and continuously stirring for 30min to obtain a mixed solution B;
(3) Regulating the pH value of the mixed solution B in the step (2) to 10 by using NaOH, and continuously stirring for 30min at 300r/min to obtain a precipitate;
(4) Calcining the precipitate obtained in the step (3) in a muffle furnace, raising the temperature to 400 ℃ at a heating rate of 5 ℃/min, and maintaining the temperature for 3 hours to obtain a product, namely the manganese oxide catalyst.
200mg of the manganese-based catalyst prepared in comparative example 1 was taken and measured to be non-conductive and have no electrocaloric catalytic oxidation effect.
Comparative example 2:
(1) Directly dissolving 5mmol of indium nitrate and 1mmol of stannous chloride into 2500mmol of deionized water to obtain a mixed solution A;
(2) Regulating the pH value of the mixed solution A in the step (1) to 10 by NaOH, and continuously stirring at 300r/min for 30min to obtain a precipitate;
(4) Calcining the precipitate obtained in the step (3) in a muffle furnace, raising the temperature to 400 ℃ at a heating rate of 5 ℃/min, and maintaining the temperature for 3 hours to obtain a product, namely the catalyst.
200mg of the catalyst prepared in comparative example 2 was taken and its electrical conductivity was measured, but no effect of catalytic oxidation of toluene was observed.
The experimental results of the above examples 1 to 7 and comparative examples 1 to 2 are shown in the following table 1:
table 1 shows the catalytic oxidation of toluene T using the Mn-based electrothermal catalyst prepared in all examples 20％ 、T 50％ And T 90％ Performance comparison table.
Table 1:
in summary, the invention synthesizes the conductive metal oxide catalyst and uses the catalyst as a catalytic material of toluene VOC, directly utilizes the piezoelectric force to promote the conductive catalyst to emit heat, thereby greatly reducing the activation temperature of the catalyst and providing the application of the catalyst in the electrothermal catalytic oxidation of toluene.
The description and practice of the invention disclosed herein will be readily apparent to those skilled in the art, and may be modified and adapted in several ways without departing from the principles of the invention. Accordingly, modifications or improvements may be made without departing from the spirit of the invention and are also to be considered within the scope of the invention.
Claims (5)
1. The preparation method of the manganese-based electrothermal catalyst for toluene purification is characterized by comprising the following specific steps:
s1, directly mixing and dissolving manganese salt, indium salt and tin salt in a certain proportion into deionized water to obtain a mixed solution A;
s2, adding a certain amount of potassium permanganate into the mixed solution A obtained in the step S1, and stirring and reacting for a period of time to obtain a mixed solution B;
s3, regulating and controlling the pH value of the mixed solution B obtained in the step S2 by using a pH regulator, and stirring and reacting for a period of time to obtain a precipitate;
s4, placing the precipitate obtained in the step S3 into a muffle furnace for calcination, heating to a certain temperature at a certain heating rate, and maintaining for a period of time to obtain the manganese-based electrothermal catalyst;
in the step S1, manganese salt is one or a mixture of a plurality of manganese nitrate, manganese chloride, manganese acetate and manganese sulfate;
in the step S1, the molar ratio of manganese salt to indium salt to tin salt to deionized water is 10 (1-5) (5-1) (1000-6000);
in the step S2, the molar ratio of the potassium permanganate to the manganese salt in the step S1 is (1-10): 1, the stirring time is 10-120 min, and the stirring speed is 100-1000 r/min.
2. The method for preparing a manganese-based electrothermal catalyst for toluene purification according to claim 1, wherein in step S1, the indium salt is one or more of indium chloride, indium nitrate, indium sulfate, and indium acetate.
3. The method for preparing a manganese-based electrothermal catalyst for toluene purification according to claim 1, wherein in step S1, the tin salt is one or more of solid tin acetate, tin sulfate, stannous chloride and tin nitrate.
4. The method for preparing a manganese-based electrothermal catalyst for purifying toluene according to claim 1, wherein in the step S3, the pH adjuster is one or a mixture of sodium hydroxide, potassium hydroxide, ammonia water and sodium ethoxide, the pH adjusting range is 9-13, the stirring time is 10-120 min, and the stirring rate is 100-1000 r/min.
5. The method for preparing a manganese-based electrothermal catalyst for toluene purification according to claim 1, wherein in step S4, the calcination temperature rise rate is 1 to 10 ℃/min, the constant temperature for calcination is 100 to 500 ℃, and the maintenance time for the constant temperature stage of calcination is 1 to 12 hours.
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